Supporting Information

Electronic Supplementary Material (ESI) for Physical Chemistry Chemical Physics. This journal is the Owner Societies 2018 Supporting Information Fluorine Substituent Effect on the Stereochemistry of Catalyzed and non- Catalyzed Diels-Alder Reactions. The Case of R-Butenone with Cyclopentadiene: A Computational Assessment of the Mechanism MERZOUD Lynda, a,b SAAL Amar, a, b MOUSSAOUI Ramdane, c OUAMERALI Ourida a, MORELL Christophe d, CHERMETTE Henry d a Laboratory of Computational and Theoretical Chemistry and Photonics, USTHB University, 16111, Algeria; b Département de Chimie, UMMTO University of Tizi Ouzou, 15000, Algeria. c Laboratoire de chimie Appliquée et de Génie Chimique, Université M. Mammeri, Tizi Ouzou, Algeria. d Université de Lyon, Université Claude Bernard Lyon 1, ENS-Lyon, Institut des Sciences Analytiques, UMR CNRS 5280, 69622 Villeurbanne Cedex, France Corresponding author: 1. Geometry Evolution: 1

Figure S.1. IRC pathways of H12-Uncatalyzed and H12-Catalyzed reactions. The variation of the interatomic distances curves C4C15 (green) and C3C13 (red) along the reaction coordinate are plotted in the same graph as energies (blue). 2

Figure S.2. IRC pathways of F11-Uncatalyzed and F11-Catalyzed reactions. The variation of the interatomic distances curves C4C15 (green) and C3C13 (red) along the reaction coordinate are plotted in the same graph as energies (blue). 3

Figure S.3. IRC pathways of F12-Uncatalyzed and F12-Catalyzed reactions. The variation of the interatomic distances curves C4C15 (green) and C3C13 (red) along the reaction coordinate are plotted in the same graph as energies (blue). 2. Energetics Table S.1. The designation and the activation energy (kcal/mol) for the catalyzed and uncatalyzed studied reactions. Reaction R structure Ea (kcal/mol) Dienophile Adduct (endo/exo) uncatalyzed catalyzed H11 H cis endo 18.3 5.1 H12 H cis exo 18.7 7.1 F11 F cis endo 19.3 9.1 F12 F cis exo 17.9 6.0 4

Figure S.4. Energy diagram corresponding to F11 and F12 reactions (with and without AlCl 3 catalyst). The calculations were performed at B3LYP/6-31G(d) level with ZPE correction. 3. Comparative ASM/EDA diagrams Table S.2. Interaction energies given in kcal/mol for the uncatalyzed transition states Endo-cis Exo-cis H F H F Pauli Repulsion 111.93 118.24 112.58 123.39 Electrostatic Interaction -53.43-61.20-52.78-56.10 Orbital Interaction -63.62-64.99-62.96-66.03 Dispersion -9.31-8.81-5.66-8.94 5

Figure S.5. Comparative activation-strain diagrams for the AlCl 3 -catalyzed (dashed lines) and uncatalyzed (solid lines) Diels-Alder reactions between cyclopentadiene and butenone (left) and between the cyclopentadiene and 3-fluorobutenone (right) along the reaction coordinate projected onto the forming C--C bond distance, computed at BLYP-D3/TZ2P level. Figure S.6. Comparative energy decomposition analysis diagram for the AlCl 3 -catalyzed (dashed lines) and uncatalyzed (solid lines) Diels-Alder reactions between cyclopentadiene and butenone (left) and between the cyclopentadiene and 3-fluorobutenone (right) along the reaction coordinate projected onto the forming C--C bond distance, computed at BLYP-D3/TZ2P level. 6

4. Dual Descriptor Scheme S.1. Dual descriptor of the interactions between cyclopentadiene and AlCl 3 - catalyzed 3-R-butenone sites in its ground state. Blue lobes correspond to positive values of the dual descriptor, whereas orange lobes correspond to negative ones. Reactants Transition Structures H-endo-cis H-exo-cis F-endo-cis F-exo-cis 7

5. NBO analysis: NBO_F_endo-cis (R1=F) Table S.4. Second order perturbation theory analysis of Fock matrix in NBO basis of the F_endo_cis (R1=F) reactant: E(2) in kcal/mol is the hyperconjugative interaction energy, εj εi is the energy difference between the donor NBO (i) and the acceptor NBO (j)and Fij is the Fock matrix element between the NBO orbitals i and j. εj εi and Fij are given in atomic units. NBO(i) NBO(j) Donor Occupation Acceptor Occupation E (2) ε j - ε i F i,j π* C 3 =O 8 0.144 π* C 1 =C 2 0.113 53.7 0.02 0.072 lp2 O 8 1.883 σ* C 2 - C 3 0.081 21.5 0.68 0.109 lp3 F 7 1.924 π* C 1 =C 2 0.113 20.95 0.44 0.086 lp2 O 8 1.883 σ* C 3 - C 4 0.054 19.84 0.65 0.103 lp1 O 8 1.978 Ry*1 C3 0.018 15.75 1.47 0.136 σ C 1 - H 6 1.973 σ* C 2 - F 7 0.042 9.27 0.78 0.076 lp1 F 7 1.988 Ry*1 C 2 0.011 8.09 1.87 0.110 lp2 F 7 1.965 σ* C 2 - C 3 0.081 7.3 0.83 0.070 cr 1 O 8 1.999 Ry*1 C 3 0.018 6.08 19.66 0.310 lp2 F 7 1.965 σ* C 1 - C 2 0.017 5.34 1.05 0.067 π* C 1 =C 2 0.113 π* C 13 =C 14 0.117 1.06 0.02 0.013 lp3 F 7 1.924 σ* C 12 - H 22 0.016 0.53 0.86 0.019 π* C 1 =C 2 0.113 π* C 15 =C 16 0.120 0.49 0.02 0.008 π C 3 =O 8 1.974 π* C 15 =C 16 0.120 0.26 0.42 0.010 π C 1 =C 2 1.906 π* C 13 =C 14 0.117 0.25 0.34 0.008 π C 1 =C 2 1.906 σ* C 12 - H 21 0.014 0.19 0.73 0.011 σ C 1 - H 5 1.982 π* C 13 =C 14 0.117 0.19 0.59 0.010 lp2 F 7 1.965 σ* C 12 - H 22 0.017 0.19 0.86 0.011 σ C 1 - H 5 1.982 Ry*2 C 13 0.002 0.14 1.31 0.012 lp1 F 7 1.988 σ* C 12 - H 22 0.016 0.14 1.49 0.013 π C 1 =C 2 1.906 σ* C 12 - H 22 0.016 0.08 0.75 0.007 π C 1 =C 2 1.906 π* C 15 =C 16 0.120 0.08 0.34 0.005 σ C 2 - C 3 1.984 Ry*2 C 16 0.002 0.08 1.43 0.010 lp3 F 7 1.924 π* C 15 =C 16 0.120 0.08 0.46 0.005 σ C 1 - C 2 1.991 Ry*1 C 13 0.003 0.06 2.08 0.010 σ C 1 - C 2 1.991 Ry*1 H 22 0.002 0.06 1.48 0.009 σ C 1 - H 5 1.982 Ry*4C 13 0.001 0.06 1.72 0.009 8

σ C 1 - H 6 1.974 Ry*2 C 13 0.002 0.06 1.30 0.008 σ C 2 - C 3 1.984 Ry*3 C 16 0.002 0.06 1.37 0.008 lp3 F 7 1.924 Ry*2 C 16 0.002 0.06 1.15 0.008 lp3 F 7 1.924 Ry*1 H 22 0.002 0.06 1.12 0.008 σ C 1 - C 2 1.991 Ry*1 C 12 0.003 0.05 1.59 0.008 σ C1 - H 6 1.974 Ry*3 C 14 0.001 0.05 1.58 0.008 NBO_F_exo-cis (R1=F) Table S.5. Second order perturbation theory analysis of Fock matrix in NBO basis of the F_exo_cis (R1=F) reactant: E(2) in kcal/mol is the hyperconjugative interaction energy, εj εi is the energy difference between the donor NBO (i) and the acceptor NBO (j)and Fij is the Fock matrix element between the NBO orbitals i and j. εj εi and Fij are given in atomic units. NBO(i) NBO(j) Donor Occupation Acceptor Occupation E (2) ε j - ε i F i,j π* C 3 =O 8 0.145 π* C 1 =C 2 0.110 39.27 0.02 0.072 lp3 F 7 1.921 π* C 1 =C 2 0.110 21.78 0.43 0.088 lp2 O 8 1.885 σ* C 2 - C 3 0.081 20.86 0.68 0.107 lp2 O 8 1.885 σ* C 3 - C 4 0.052 19.76 0.65 0.103 π C 1 =C 2 1.905 π* C 3 =O 8 0.145 17.53 0.30 0.066 lp1 O 8 1.977 Ry*1 C 3 0.018 15.49 1.46 0.134 σ C 1 - H 5 1.974 σ* C 2 - F 7 0.041 9.08 0.80 0.076 lp1 F 7 1.989 Ry*1 C 2 0.011 8.3 1.87 0.111 lp2 F 7 1.965 σ* C 2 - C 3 0.081 7.31 0.82 0.070 cr1 O 8 1.999 Ry*1 C 3 0.018 6.06 19.65 0.309 σ C 1 - H 6 1.982 σ* C 2 - C 3 0.081 6 0.95 0.069 lp2 F 7 1.965 σ* C 1 - C 2 0.017 5.71 1.05 0.069 π* C 1 =C 2 0.110 π* C 13 =C 14 0.117 0.82 0.02 0.011 π C 3 =O 8 1.975 σ* C 12 - H 22 0.018 0.54 0.84 0.019 lp2 O 8 1.885 σ* C 12 - H 22 0.018 0.53 0.73 0.018 π* C 3 =O 8 0.145 π* C 15 =C 16 0.122 0.48 0.04 0.011 lp1 O 8 1.977 σ* C 12 - H 22 0.018 0.29 1.16 0.016 lp3 F 7 1.921 π* C 15 =C 16 0.122 0.28 0.46 0.010 lp3 F 7 1.921 Ry*3 C 15 0.001 0.15 1.26 0.013 π C 1 =C 2 1.905 π* C 13 =C 14 0.117 0.14 0.35 0.006 π C 3 =O 8 1.976 π* C 15 =C 16 0.122 0.13 0.43 0.007 π C 1 =C 2 1.905 σ* C 12 - H 21 0.014 0.12 0.73 0.009 σ C 2 - C 3 1.984 Ry*2 C 16 0.002 0.11 1.42 0.011 σ C 1 - H 5 1.974 π* C 13 =C 14 0.117 0.08 0.59 0.006 σ C 1 - H 5 1.974 Ry*2 C 13 0.002 0.07 1.29 0.008 π C 1 =C 2 1.905 σ* C 12 - H 22 0.018 0.06 0.76 0.006 σ C 2 - C 3 1.984 Ry*3 C 16 0.002 0.06 1.40 0.008 σ C 2 - C 3 1.984 Ry*4 C 16 0.001 0.06 1.88 0.009 9

σ C 2 - F 7 1.995 Ry*3 C 15 0.001 0.06 1.86 0.009 σ C 1 - H 5 1.974 σ* C 12 - H 22 0.018 0.05 1.00 0.007 σ C 1 - H 6 1.982 Ry*2 C 13 0.002 0.05 1.29 0.007 NBO_H_endo-cis (R1=H) Table S.6. Second order perturbation theory analysis of Fock matrix in NBO basis of the H_endo_cis (R1=H) reactant: E(2) in kcal/mol is the hyperconjugative interaction energy, εj εi is the energy difference between the donor NBO (i) and the acceptor NBO (j)and Fij is the Fock matrix element between the NBO orbitals i and j. εj εi and Fij are given in atomic units. NBO(i) Occupatio Donor n NBO(j) Acceptor Occupation E (2) ε j - ε i F i,j π* C 3 =O 8 0.145 π* C 1 =C 2 0.046 41.89 0.01 0.071 lp2 O 8 1.886 σ* C 3 - C 4 0.054 20.61 0.64 0.104 lp2 O 8 1.886 σ* C 2 - C 3 0.065 20 0.69 0.106 π C 1 =C 2 1.899 π* C 3 =O 8 0.145 19.32 0.30 0.069 lp1 O 8 1.977 Ry*1 C 3 0.018 16.4 1.49 0.140 cr1 O 8 1.999 Ry*1 C 3 0.018 6.23 19.68 0.314 σ C 1 - H 6 1.985 σ* C 2 - H 7 0.016 5.25 0.99 0.064 σ C 1 - C 2 1.989 Ry*4 C 12 0.001 0.05 2.48 0.010 σ C 1 - C 2 1.989 Ry*1 C 13 0.003 0.06 2.06 0.010 π C 1 =C 2 1.899 σ* C 12 - H 21 0.014 0.23 0.71 0.012 π C 1 =C 2 1.899 σ* C 12 - H 22 0.015 0.19 0.72 0.011 π C 1 =C 2 1.899 π* C 13 =C 14 0.116 0.27 0.33 0.008 π C 1 =C 2 1.899 π* C 15 =C 16 0.120 0.15 0.32 0.006 σ C 1 - H 5 1.987 Ry*2 C 13 0.002 0.11 1.31 0.011 σ C 1 - H 5 1.987 π* C 13 =C 14 0.116 0.15 0.59 0.009 σ C 1 - H 6 1.985 Ry*2 C 13 0.002 0.12 1.30 0.011 σ C 2 - C 3 1.983 Ry*2 C 16 0.002 0.08 1.40 0.009 π C 3 =O 8 1.974 π* C 13 =C 14 0.116 0.06 0.41 0.005 π C 3 =O 8 1.974 π* C 15 =C 16 0.120 0.5 0.41 0.013 lp2 O 8 1.886 π* C 13 =C 14 0.116 0.12 0.30 0.005 π* C 3 =O 8 0.145 π* C 13 =C 14 0.116 0.05 0.03 0.003 NBO_H_exo-cis (R1=H) Table S.7. Second order perturbation theory analysis of Fock matrix in NBO basis of the H_exo_cis (R1=H) reactant: E(2) in kcal/mol is the hyperconjugative interaction energy, εj εi is the energy difference between the donor NBO (i) and the acceptor NBO (j)and Fij is the Fock matrix element between the NBO orbitals i and j. εj εi and Fij are given in atomic units. 10

NBO(i) NBO(j) Donor Occupation Acceptor Occupation E (2) ε j - ε i F i,j π* C 3 =O 8 0.149 π* C 1 =C 2 0.047 27.91 0.02 0.071 lp2 O 8 1.887 σ* C 3 - C 4 0.054 20.56 0.64 0.104 π C 1 =C 2 1.896 π* C 3 =O 8 0.149 19.92 0.29 0.069 lp2 O 8 1.887 σ* C 2 - C 3 0.063 18.99 0.70 0.104 lp1 O 8 1.976 Ry*1 C 3 0.017 15.86 1.48 0.137 cr1 O 8 1.999 Ry*1 C 3 0.017 6.17 19.67 0.312 σ C 1 - H 6 1.987 σ* C 2 - C 3 0.063 5.12 0.98 0.064 σ C 1 - H 5 1.985 σ* C 2 - H 7 0.016 5.08 0.99 0.063 π C 3 =O 8 1.974 σ* C 12 - H 22 0.021 1.12 0.84 0.027 lp2 O 8 1.887 σ* C 12 - H 22 0.021 0.96 0.73 0.024 lp1 O 8 1.976 σ* C 12 - H 22 0.021 0.61 1.15 0.024 π* C 3 =O 8 0.149 π* C 15 =C 16 0.123 0.56 0.03 0.010 σ C 1 - H 5 1.985 π* C 13 =C 14 0.122 0.2 0.58 0.010 π C 1 =C 2 1.896 π* C 13 =C 14 0.122 0.19 0.32 0.007 π C 1 =C 2 1.896 σ* C 12 - H 21 0.013 0.17 0.71 0.010 σ C 1 - H 5 1.985 Ry*2 C 13 0.002 0.12 1.27 0.011 σ C 2 - C 3 1.984 Ry*3 C 16 0.002 0.09 1.40 0.010 σ C 1 - H 5 1.985 σ* C 12 - H 22 0.021 0.07 1.00 0.007 π C 3 =O 8 1.975 π* C 15 =C 16 0.123 0.07 0.42 0.005 σ C 1 - C 2 1.989 Ry*4 C 12 0.001 0.06 2.31 0.011 σ C 1 - H 5 1.985 Ry*4 C 13 0.001 0.06 1.70 0.009 NBO_F_endo-cis (R2=F) Table S.8. Second order perturbation theory analysis of Fock matrix in NBO basis of the F_endo_cis (R2=F) reactant: E(2) in kcal/mol is the hyperconjugative interaction energy, εj εi is the energy difference between the donor NBO (i) and the acceptor NBO (j)and Fij is the Fock matrix element between the NBO orbitals i and j. εj εi and Fij are given in atomic units. NBO(i) NBO(j) Donor Occupation Acceptor Occupation E (2) ε j - ε i F i,j lp3 F 5 1.897 π* C 1 =C 2 0.125 24.73 0.44 0.094 lp2 O 8 1.887 σ* C 3 - C 4 0.054 20.3 0.64 0.103 lp2 O 8 1.887 σ* C 2 - C 3 0.060 20.16 0.70 0.107 π C 1 =C 2 1.888 π* C 3 =O 8 0.164 20.07 0.31 0.072 lp1 O 8 1.977 Ry*1 C 3 0.018 16.37 1.50 0.140 lp2 F 5 1.971 σ* C 1 - H 6 0.026 6.85 0.89 0.070 σ C 4 - H 10 1.968 π* C 3 =O 8 0.164 6.33 0.53 0.053 cr1 O 8 1.999 Ry*1 C 3 0.018 6.2 19.69 0.313 lp2 F 5 1.971 σ* C 1 - C 2 0.018 6 1.06 0.071 lp1 F 5 1.991 Ry*1 C 1 0.008 5.9 1.78 0.092 11

π* C 1 =C 2 0.125 π* C 13 =C 14 0.117 0.95 0.03 0.014 π C 3 =O 8 1.976 π* C 15 =C 16 0.117 0.37 0.42 0.011 lp3 F 5 1.897 σ* C 12 - H 22 0.016 0.36 0.87 0.016 π* C 1 =C 2 0.125 π* C 15 =C 16 0.117 0.26 0.03 0.007 π C 1 =C 2 1.888 π* C 13 =C 14 0.117 0.22 0.35 0.008 π C 3 =O 8 1.976 π* C 13 =C 14 0.117 0.19 0.42 0.008 π C 1 =C 2 1.888 σ* C 12 - H 21 0.014 0.16 0.74 0.010 σ C 1 - H 6 1.984 Ry*3 C 13 0.002 0.16 1.32 0.013 π* C 3 =O 8 0.165 π* C 15 =C 16 0.117 0.16 0.03 0.005 lp2 O 8 1.887 π* C 13 =C 14 0.117 0.15 0.30 0.006 π C 1 =C 2 1.888 π* C 15 =C 16 0.117 0.12 0.35 0.006 π C 1 =C 2 1.888 σ* C 12 - H 22 0.016 0.11 0.75 0.008 lp2 F 5 1.971 σ* C 12 - H 22 0.016 0.09 0.88 0.008 π* C 3 =O 8 0.164 π* C 13 =C 14 0.117 0.09 0.03 0.004 σ C 1 - H 6 1.984 Ry*4 C 13 0.001 0.08 1.74 0.010 lp1 F 5 1.991 σ* C 12 - H 22 0.016 0.08 1.50 0.010 σ C 1 - H 6 1.984 π* C 13 =C 14 0.117 0.07 0.62 0.006 π C 1 =C 2 1.888 Ry*3 C 13 0.002 0.06 1.05 0.007 lp1 O 8 1.977 π* C 13 =C 14 0.117 0.06 0.73 0.006 lp3 F 5 1.897 Ry*2 C 13 0.002 0.05 1.11 0.007 NBO_F_exo-cis (R2=F) Table S.9. Second order perturbation theory analysis of Fock matrix in NBO basis of the F_exo_cis (R2=F) reactant: E(2) in kcal/mol is the hyperconjugative interaction energy, εj εi is the energy difference between the donor NBO (i) and the acceptor NBO(j) and Fij is the Fock matrix element between the NBO orbitals i and j. εj εi and Fij are given in atomic units. NBO(i) NBO(j) Donor Occupation Acceptor Occupation E (2) ε j - ε i F i,j π* C 3 =O 8 0.167 π* C 1 =C 2 0.129 86.69 0.01 0.071 lp3 F 5 1.896 π* C 1 =C 2 0.129 25.05 0.44 0.094 π C 1 =C 2 1.883 π* C 3 =O 8 0.167 20.58 0.31 0.072 lp2 O 8 1.889 σ* C 3 - C 4 0.053 20.31 0.64 0.104 lp2 O 8 1.889 σ* C 2 - C 3 0.059 19.23 0.71 0.105 lp1 O 8 1.975 Ry*1 C 3 0.017 15.82 1.48 0.137 lp2 F 5 1.970 σ* C 1 - H 6 0.026 7.04 0.88 0.070 lp2 F 5 1.970 σ* C 1 - C 2 0.018 6.26 1.05 0.073 cr1 O 8 1.999 Ry*1 C 3 0.017 6.16 19.67 0.312 lp1 F 5 1.991 Ry*1 C 1 0.009 6.15 1.79 0.094 π C 3 =O 8 1.976 σ* C 12 - H 22 0.021 1.28 0.85 0.029 lp2 O 8 1.889 σ* C 12 - H 22 0.021 0.96 0.74 0.024 π* C 1 - C 2 0.129 π* C 13 =C 14 0.126 0.86 0.03 0.012 lp1 O 8 1.975 σ* C 12 - H 22 0.021 0.71 1.16 0.026 12

π* C 3 =O 8 1.976 π* C 15 =C 16 0.123 0.43 0.04 0.009 lp3 F 5 1.896 π* C 13 =C 14 0.126 0.22 0.47 0.009 σ C 1 - H 6 1.985 π* C 13 =C 14 0.126 0.21 0.62 0.010 π C 1 =C 2 1.884 π* C 13 =C 14 0.126 0.19 0.35 0.007 π C 1 - C 2 1.884 σ* C 12 - H 21 0.014 0.15 0.74 0.010 lp3 F 5 1.896 Ry*3 C 14 0.001 0.15 1.22 0.012 σ C 1 - H 6 1.985 Ry*3 C 13 0.002 0.12 1.30 0.011 σ C 1 - H 6 1.985 Ry*4C 13 0.001 0.09 1.73 0.011 π* C 1 =C 2 0.129 π* C 15 =C 16 0.123 0.09 0.03 0.004 σ C 2 - C 3 1.978 Ry*2 C 16 0.002 0.08 1.40 0.010 σ C 1 - F 5 1.996 Ry*3 C 14 0.001 0.07 1.83 0.010 σ C 1 - H 6 1.985 Ry*2 C 13 0.002 0.07 1.33 0.009 σ C 1 - C 2 1.990 Ry*3 C 14 0.001 0.06 1.57 0.008 π C 1 =C 2 1.884 Ry*2 C 13 0.002 0.06 1.06 0.007 π C 3 =O 8 1.976 π* C 15 =C 16 0.123 0.06 0.42 0.004 lp3 F 5 1.897 Ry*2 C 13 0.002 0.05 1.18 0.007 6. State Specific Dual Descriptors Scheme S.2. State-specific dual descriptor of the interactions between cyclopentadiene and R- butenone for exo orientation. Blue lobes correspond to positive values of the dual descriptor, whereas orange lobes correspond to negative ones calculated at the TD-B3LYP/6-31G(d,p) level. 13

Scheme S.3. State-specific dual descriptor of the interactions of catalyzed and uncatalyzed Diels- Alder reaction between cyclopentadiene and 3-R-butenone for exo orientation. Blue lobes correspond to positive values of the dual descriptor, whereas orange lobes correspond to negative ones calculated at the TD-B3LYP/6-31G(d,p) level. R1=H R1=F 7. Domains Table S.10. Electrostatic interaction energy of the excited states in u.a and activation energy in kcal/mol and numerical values from the condensation of the nucleophilic domains for oxygen atom in u.a. are given for the exo reactions between the cyclopentadiene and R-butenone. s(d O ) is the integrated value of the domain volume. E PSCube Ea s(d O ) R1=H 0.115 18.7-0.016 R1=F 0.121 17.9-0.015 R2=F 0.062 16.9-0.272 14

8. Geometric Structures Uncatalyzed Reactant_H_endo-cis (R1=H) H -1.07240400 1.47439100-1.45250300 C -0.95563100 1.77783600-0.41667000 C 0.22668200 1.63351400 0.19308800 C 1.39431000 1.05054100-0.52432700 C 2.72678800 1.10548200 0.20251300 H -1.81687800 2.21241200 0.08232800 H 0.37434100 1.95090100 1.22362900 O 1.29539200 0.57251100-1.64524900 H 3.49484900 0.60252700-0.38812100 H 3.02191400 2.15027700 0.36719800 H 2.64877300 0.63433500 1.18997400 C -2.12827600-0.94999400 0.07834800 C -1.17951400-1.50386500-0.70876900 C 0.01454700-1.77588400 0.09266400 C -0.20184600-1.38280300 1.36713500 C -1.60858800-0.85785700 1.48987400 H -3.12606700-0.64846000-0.22011100 H -1.26039700-1.70799800-1.77085800 H 0.92659900-2.20930400-0.30281500 H 0.48782900-1.46572200 2.19981600 H -2.20549000-1.48275700 2.17392900 H -1.65014100 0.16148700 1.89516000 Uncatalyzed Product_H_endo-cis (R1=H) H -1.03554600 1.23264100-1.32319700 C -1.20010600 1.01272200-0.26645300 C 0.14182900 0.80757600 0.48655400 C 1.35322100 0.84188400-0.42971100 C 2.69942700 1.15528300 0.20184900 H -1.77921000 1.83132600 0.17720400 H 0.27366700 1.52464300 1.30578900 O 1.26216400 0.58131600-1.61626400 H 3.49863500 0.69546900-0.38438200 H 2.85559700 2.24259600 0.19622600 H 2.75488700 0.82361200 1.24443900 C -1.93512300-0.35196000-0.04727200 C -1.12391500-1.43813300-0.73873700 C -0.01615800-1.65419100-0.01646400 C -0.03796800-0.66000800 1.13189600 C -1.55366900-0.62359000 1.42760500 H -3.00064200-0.32535400-0.29010200 H -1.36837000-1.86904600-1.70423400 H 0.82489100-2.28716000-0.27924300 H 0.63654400-0.85276600 1.96951500 H -1.92835100-1.58174800 1.80009900 H -1.84925200 0.18115300 2.11186400 Uncatalyzed TS_H_endo-cis (R1=H) H -1.10928072 1.28521897-1.39879287 C -1.10928072 1.28521897-0.31359687 C 0.14194028 1.28521897 0.31251313 15

C 1.33118928 0.94540097-0.46227787 C 2.69072028 1.13904297 0.19851113 H -1.91911772 1.84673597 0.14646713 H 0.26265928 1.65538997 1.32633713 O 1.24772628 0.52394397-1.61862987 H 3.45256428 0.59489397-0.36445487 H 2.95538628 2.20484197 0.19632513 H 2.68952528 0.80584697 1.24253913 C -1.94432072-0.53067303-0.01533387 C -1.11344872-1.40771303-0.73956987 C 0.01011028-1.73547703 0.04458213 C -0.11544572-1.14016703 1.28594513 C -1.53547172-0.67304503 1.44266713 H -2.97568772-0.34178003-0.30163387 H -1.24405172-1.67666503-1.78159487 H 0.87899628-2.27507303-0.31433187 H 0.58743328-1.22917903 2.10672713 H -2.12834972-1.48992803 1.88842113 H -1.67748272 0.21310897 2.06491113 Uncatalyzed Reactant_H_exo-cis (R1=H) C 2.54614400 0.18037300-0.46662900 C 1.81232800 1.42133800-0.21683200 C 0.99540500 1.24990500 0.84757600 C -0.94087100-0.33101600-1.20959600 C -0.20268600-1.44219800-1.31560900 C 2.17424300-0.74790000 0.44400800 H 3.26523100 0.04283000-1.26817900 H 1.91996900 2.32702400-0.80566800 H 0.33803000 1.99116600 1.28830200 C -1.94822800-0.16155200-0.12822500 H 0.51605400-1.58252300-2.11554800 H -0.32361100-2.25202000-0.60075000 H 2.54748200-1.76257800 0.52656000 O -2.02253100-0.92744200 0.82467100 C 1.17591100-0.14030400 1.39218100 H 0.23425500-0.70131800 1.45120900 H 1.57637600-0.11059000 2.41861800 H -0.84536600 0.47457800-1.93373200 C -2.90098100 1.01110200-0.27619500 H -2.34069100 1.95072700-0.35969000 H -3.48880400 0.90742500-1.19748400 H -3.57394100 1.05655500 0.58202000 Uncatalyzed Product_H_exo-cis (R1=H) C 2.45031100 0.18242100-0.54582600 C 1.75786000 1.31168200-0.34011000 C 0.49418400 0.93484600 0.41648200 C -0.42018500 0.13248300-0.61964000 C 0.39109200-1.18042500-0.82238300 C 1.65975400-0.96204200 0.07276200 H 3.35504100 0.06543500-1.13471600 H 1.97498300 2.30237200-0.72729000 16

H -0.02412900 1.74831900 0.93082900 C -1.79326300-0.06379400 0.01058400 H 0.64670700-1.34968500-1.87171200 H -0.18495700-2.03720900-0.45959000 H 2.21905100-1.87758200 0.28044200 O -2.03104100-0.97439900 0.78542500 C 1.01805900-0.23618500 1.27900800 H 0.22450200-0.81270400 1.76192700 H 1.75394200 0.09226200 2.01902200 H -0.52584800 0.71192300-1.54252700 C -2.85518900 0.97072400-0.32725100 H -2.42691300 1.96874600-0.46969300 H -3.33899400 0.68851600-1.27234000 H -3.61670800 0.99228400 0.45552600 Uncatalyzed TS_H_exo-cis (R1=H) C 2.44793610 0.16628144-0.52543088 C 1.79557310 1.38149044-0.25251988 C 0.79676610 1.15769044 0.68724612 C -0.66474990-0.15345356-0.94536888 C 0.17973210-1.26840656-1.00558488 C 1.80494310-0.86806556 0.18355312 H 3.22099310 0.02533844-1.27415188 H 1.98523710 2.32224244-0.75924888 H 0.16005610 1.91888644 1.12430612 C -1.83177090-0.12285556-0.05967188 H 0.71159110-1.47553456-1.92830388 H -0.13769490-2.14972856-0.45366188 H 2.24180610-1.85520956 0.30692312 O -2.01315790-0.95050056 0.83571212 C 1.01062610-0.19943656 1.28821912 H 0.10379910-0.71828356 1.60555512 H 1.66984010-0.09186956 2.16683312 H -0.59898490 0.61639944-1.70768088 C -2.85591290 0.97816344-0.31043788 H -2.37506190 1.94777744-0.48296488 H -3.44155390 0.74262844-1.20893188 H -3.53747290 1.04541644 0.54033912 Catalyzed Reactant_H_endo-cis (R1=H) C -4.32496400-0.20537500 0.40612200 C -3.30355700-0.00572300 1.49400300 C -2.26118700-0.84442900 1.28817800 C -2.49221900-1.60848000 0.06198200 C -3.67662800-1.23604100-0.48220400 C -2.17970000 0.88898500-2.07324200 C -1.80170000 1.75835300-1.11325100 C -0.57363500 1.56643600-0.36399200 C -0.12939800 2.57261300 0.65040500 H -4.57361700 0.72551400-0.12322500 H -5.27562300-0.57796500 0.81846600 H -3.43294000 0.67556500 2.32749300 H -1.38364300-0.95038300 1.91694500 17

H -1.80630200-2.35169600-0.33067600 H -4.14033800-1.64884600-1.37106600 H -1.55773300 0.03953400-2.33201000 H -3.09171400 1.03679800-2.64254600 H -2.40234500 2.62764100-0.86580400 O 0.13321700 0.55041900-0.60715600 H -0.85874700 3.37225200 0.79058700 H 0.06846200 2.06918100 1.60316100 H 0.82696000 3.00007200 0.32133500 Al 1.74288600-0.22403300-0.04190100 Cl 1.69146300-2.12447100-1.00396600 Cl 1.59012200-0.32784900 2.09877700 Cl 3.22431600 1.14926400-0.74136900 Catalyzed Product_H_endo-cis (R1=H) C -4.06688200-0.06314400 0.16632800 C -2.81089900 0.48887900 0.87546600 C -2.01293500-0.78238100 1.05084300 C -2.25089100-1.54654100-0.02728900 C -3.25608500-0.82364600-0.90812700 C -2.53448800 0.38581300-1.59697400 C -2.17006500 1.30993100-0.40217300 C -0.72042000 1.47004100-0.15449400 C -0.16820900 2.62897800 0.61095700 H -4.72496400 0.71314600-0.24175900 H -4.63822200-0.72482600 0.82285300 H -2.94770200 1.12958600 1.74802300 H -1.27912100-0.95447800 1.82994400 H -1.74832300-2.47034100-0.29145100 H -3.81394400-1.44790600-1.60873300 H -1.65624000 0.07830500-2.16622300 H -3.22244000 0.90113300-2.27372800 H -2.66012800 2.28615800-0.44167900 O 0.03131400 0.53458400-0.51252800 H -0.90409700 3.42045900 0.76127800 H 0.18303500 2.26107700 1.58530200 H 0.71552400 3.01975700 0.09391300 Al 1.67277700-0.23960500-0.02582200 Cl 1.61769200-2.14836900-0.96228700 Cl 1.57574900-0.32882000 2.12065300 Cl 3.13135500 1.12843200-0.76667900 Catalyzed TS_H_endo-cis (R1=H) C -3.98735400-0.14545200 0.26571900 C -3.02155200-0.00082100 1.40328200 C -1.98161500-0.87354900 1.24061800 C -2.09862500-1.50007000-0.03784200 C -3.18100700-0.95797300-0.73177500 C -2.24835700 0.60085400-1.81862400 C -1.82274400 1.58835400-0.92671900 C -0.55828600 1.50014700-0.30864600 C -0.02936900 2.57921100 0.58886800 H -4.40068500 0.79625300-0.10572400 18

H -4.84441000-0.75396900 0.59901700 H -3.18940000 0.63930800 2.26229500 H -1.16150100-1.03222500 1.93126400 H -1.40095600-2.23365600-0.42763500 H -3.63406500-1.44369200-1.59015000 H -1.50039700-0.03312600-2.28033600 H -3.13515300 0.78713600-2.41750900 H -2.45680400 2.43369800-0.68335800 O 0.16007600 0.45951800-0.54218600 H -0.74838200 3.39062400 0.72213100 H 0.23746400 2.15580500 1.56369400 H 0.89610100 2.98090900 0.15799300 Al 1.77854100-0.24953900-0.03022700 Cl 1.74924200-2.18260400-0.95691100 Cl 1.70433000-0.36820800 2.12425700 Cl 3.28231100 1.08825800-0.75855300 Catalyzed Reactant_H_exo-cis (R1=H) C 4.45976000-0.40030900-0.06493200 C 3.93713700 0.36580800 1.06429200 C 2.76155700-0.17515800 1.46629000 C 1.74189800 1.50725400-1.36421500 C 2.13670900 0.52703400-2.20286500 C 3.60095600-1.40739300-0.35881200 H 5.39364300-0.18501300-0.57445200 H 4.43282600 1.22467900 1.50496900 H 2.13970100 0.14913100 2.29275500 C 0.49941500 1.43485300-0.62062200 H 3.05804300 0.60724000-2.76837300 H 1.51984000-0.35032100-2.36989700 H 3.72593700-2.16513800-1.12401100 O -0.22685800 0.40597400-0.73039200 Al -1.81817600-0.23792000 0.03600400 Cl -1.37629100-0.23722700 2.13859000 Cl -1.99841200-2.17757200-0.82062800 Cl -3.31054200 1.17676900-0.55066000 C 2.45876700-1.38043000 0.62123800 H 1.47306000-1.33760200 0.14019700 H 2.44174900-2.29469100 1.23528300 H 2.35023300 2.39261100-1.21296100 C 0.06414300 2.57813700 0.24085400 H 0.79425200 3.38880900 0.25467900 H -0.90025100 2.95075700-0.12862400 H -0.11571600 2.21672000 1.26059500 Catalyzed Product_H_exo-cis (R1=H) C 4.42783200-0.33912100-0.11264800 C 3.97637400 0.37506300 0.94392700 C 2.52277300 0.17745400 1.01508300 C 2.00302500 1.13592200-0.69442500 C 2.50088900 0.07969000-1.65822000 C 3.25858500-1.00871900-0.78344200 H 5.44148400-0.34175900-0.50063600 19

H 4.54208400 1.06667900 1.55880900 H 1.92541600 0.54630600 1.84485200 C 0.59588400 1.32017800-0.46861700 H 3.16263100 0.50821000-2.41493800 H 1.66524800-0.40968300-2.16640200 H 3.49388700-1.90150200-1.36592100 O -0.20701400 0.36711600-0.72622600 Al -1.80609300-0.23228900 0.01088500 Cl -1.36034900-0.23555600 2.12537900 Cl -2.01555400-2.18989100-0.80471600 Cl -3.32744600 1.16402000-0.54170300 C 2.28881800-1.18635300 0.40546500 H 1.25589000-1.38807500 0.12076100 H 2.63103500-1.97365300 1.08807100 H 2.57747700 2.05561600-0.63602200 C 0.07548700 2.58202200 0.15441300 H 0.84378000 3.35357500 0.23105800 H -0.77007000 2.95156600-0.43597200 H -0.31893700 2.35745000 1.15373500 Catalyzed TS_H_exo-cis (R1=H) C 4.26934700-0.36157700-0.11706800 C 3.85582300 0.30980100 1.06159200 C 2.58301900-0.10427800 1.38661800 C 1.75836300 1.29585900-1.08800000 C 2.25249400 0.22736500-1.85202000 C 3.20893100-1.12892300-0.62010300 H 5.22987700-0.22742500-0.60457200 H 4.43917400 1.05132800 1.59591800 H 1.98784000 0.23388300 2.22738700 C 0.45332000 1.33250400-0.55579700 H 3.08746000 0.41407500-2.51915100 H 1.53611100-0.50570200-2.21253500 H 3.35113100-1.92192500-1.34781200 O -0.33398200 0.32579300-0.71590200 Al -1.91909000-0.25625300 0.02169100 Cl -1.49038600-0.26979300 2.14169200 Cl -2.13764200-2.21842400-0.79739000 Cl -3.44927200 1.13434500-0.53468000 C 2.18019800-1.22421400 0.48845400 H 1.13314800-1.21960300 0.18301400 H 2.34077000-2.17509900 1.02485700 H 2.38301400 2.16502900-0.91432900 C -0.05206800 2.55046300 0.16371000 H 0.69781100 3.34318000 0.20668500 H -0.95056300 2.92116100-0.34324100 H -0.35821800 2.27987800 1.18111400 Uncatalyzed Reactant_F_endo-cis (R1=F) H -1.07241700 1.33638300-1.65985800 C -1.01371900 1.54648300-0.60079000 C 0.14593400 1.35554800 0.02553900 C 1.39755800 0.87787600-0.62890200 20

C 2.67104600 0.97830600 0.18399300 H -1.88841900 1.92097000-0.08194000 F 0.26594200 1.60912400 1.35861100 O 1.37262500 0.46203100-1.77586200 H 3.50972000 0.62573700-0.41865200 H 2.84474100 2.01636800 0.49275000 H 2.59276500 0.38491200 1.10159000 C -2.21301800-1.16835300-0.02418300 C -1.37943200-1.71865300-0.93528400 C -0.10073100-2.02942500-0.29411400 C -0.15416000-1.67085600 1.00789300 C -1.52146700-1.12001400 1.31422500 H -3.23402100-0.84357500-0.19027400 H -1.59683700-1.89617600-1.98324400 H 0.74986700-2.46300900-0.80872800 H 0.62991200-1.78531600 1.74795500 H -2.04580000-1.74684500 2.05435000 H -1.47942700-0.11241600 1.74763800 Uncatalyzed Product_F_endo-cis (R1=F) H -1.11039900 0.99838700-1.49292400 C -1.23815800 0.79493200-0.42854500 C 0.11346600 0.56600300 0.28152100 C 1.36608700 0.69677500-0.57379600 C 2.64940500 1.06252200 0.14494700 H -1.73670400 1.64633200 0.04383800 F 0.22125100 1.47825100 1.35519100 O 1.32867200 0.42290000-1.75836700 H 3.50095000 0.82842600-0.49696500 H 2.65544600 2.13323400 0.38095900 H 2.73304500 0.53215300 1.09948600 C -2.00473600-0.54442700-0.15734700 C -1.29404000-1.62467900-0.96095700 C -0.12001800-1.87062200-0.36570700 C -0.02038500-0.93203400 0.83604400 C -1.50126800-0.88471900 1.26774000 H -3.08506800-0.47043700-0.29971500 H -1.64691300-2.02529200-1.90529400 H 0.67875100-2.51131600-0.72236600 H 0.72997100-1.16922000 1.59361800 H -1.86380400-1.85032500 1.63108200 H -1.70741700-0.10360900 2.00679500 Uncatalyzed TS_F_endo-cis (R1=F) H -1.15844369 1.04896912-1.56498778 C -1.15844369 1.04896912-0.48207478 C 0.09996431 1.04896912 0.11887522 C 1.34588431 0.78018712-0.58942078 C 2.64514531 1.02669412 0.15866422 H -1.92361269 1.66144712-0.01317978 F 0.21232631 1.55765712 1.38631322 O 1.32048831 0.38781812-1.75671278 H 3.48066731 0.71611412-0.47151778 21

H 2.74921231 2.09151912 0.40087222 H 2.67048531 0.48195112 1.10858322 C -2.01678169-0.72882088-0.12146278 C -1.30771669-1.61240988-0.96509878 C -0.10906669-1.98951288-0.33115978 C -0.07419469-1.43925788 0.93760922 C -1.44674969-0.93032888 1.27404122 H -3.06777469-0.49996088-0.27836678 H -1.56478169-1.83406188-1.99509278 H 0.69691431-2.53832988-0.80467078 H 0.71832031-1.56789988 1.66618822 H -2.01708569-1.73410188 1.76949422 H -1.46842769-0.05816188 1.93006222 Uncatalyzed Reactant_F_exo-cis (R1=F) C 2.51898200-0.53579300 0.00500500 C 1.68393900-0.88681500-1.14625200 C 1.05436100 0.22174500-1.59571300 C -0.85798600-0.40476300 0.94965200 C -0.16642400 0.12711300 1.95535700 C 2.39428800 0.78567700 0.25916800 H 3.12810400-1.24314500 0.55877500 H 1.59505900-1.88790000-1.55524400 H 0.38204200 0.29016600-2.44360300 C -1.82526400 0.33931000 0.09166400 H 0.50387900-0.47088100 2.55948900 H -0.28797500 1.17992600 2.17700100 H 2.89085300 1.34657700 1.04305400 O -1.87159100 1.55990800 0.12499500 C 1.46493600 1.40009200-0.75434400 H 0.60355100 1.90675300-0.29774100 H 1.98087100 2.16373500-1.35846700 C -2.74550800-0.49404200-0.77402100 H -3.33485800-1.17977800-0.15313700 H -3.41132500 0.16679400-1.33143000 H -2.16478300-1.11512800-1.46456100 F -0.74918800-1.72374200 0.65250400 Uncatalyzed Product_F_exo-cis (R1=F) C 2.44459300-0.58065800 0.10236300 C 1.68261600-0.97580600-0.92657000 C 0.53236300 0.00607300-1.02907500 C -0.37328700-0.26157000 0.25029000 C 0.48747000 0.28953400 1.40790900 C 1.82539200 0.68292700 0.68762800 H 3.29815900-1.10338300 0.52212100 H 1.77246300-1.88522200-1.50996100 H -0.02216500 0.01706000-1.97045500 C -1.71839700 0.40217900-0.02502700 H 0.60739300-0.47810900 2.17624500 H 0.01949200 1.17294300 1.85148700 H 2.48603600 1.30507800 1.29521800 O -1.87778100 1.59534700 0.15546700 22

C 1.22860400 1.31771000-0.59125700 H 0.53361800 2.13831100-0.39002800 H 1.98821100 1.63275300-1.31347700 C -2.78210700-0.48182400-0.64850000 H -3.23046100-1.11982200 0.12245000 H -3.55698000 0.14545000-1.09344000 H -2.35338600-1.15422300-1.39804300 F -0.60298400-1.63085500 0.44786100 Uncatalyzed TS_F_exo-cis (R1=F) C 2.39555955-0.57898254 0.07912646 C 1.67063455-0.90901754-1.08181254 C 0.85021855 0.15404946-1.42391654 C -0.62512445-0.33152654 0.68408446 C 0.28099355 0.22956046 1.58134646 C 1.95682455 0.67801646 0.54907446 H 3.06466655-1.24747554 0.61067646 H 1.69405155-1.87320054-1.57813554 H 0.19981555 0.20062546-2.29005154 C -1.72670045 0.36814046 0.02942446 H 0.70318855-0.42714654 2.33429346 H 0.04681955 1.23521146 1.91475246 H 2.51189755 1.25081246 1.28746946 O -1.83563945 1.59410946 0.10287046 C 1.25456055 1.35088346-0.61830454 H 0.43273455 2.02328446-0.36120654 H 2.00371455 1.93088646-1.18376754 C -2.74462245-0.48815054-0.70658754 H -3.30148045-1.11001754 0.00531546 H -3.44135745 0.16664746-1.23328654 H -2.26061745-1.17095554-1.41216654 F -0.63445345-1.69275554 0.58775446 Catalyzed Reactant_F_endo-cis (R1=F) C -2.20955900-2.09845900-0.12736800 C -1.84945500-1.47768200 1.14519700 C -2.85026300-0.65296500 1.53949900 C -1.85082600 1.40603500-0.87999400 C -2.14038100 0.67157700-1.96469000 C -3.43327000-1.65628900-0.51128900 H -1.57829400-2.79838400-0.66425100 H -0.91924100-1.65710900 1.67325900 H -2.88729100-0.07010800 2.45287900 C -0.60783000 1.30377100-0.12584600 H -1.41148300-0.02832200-2.34881800 H -3.07774900 0.80436400-2.49179800 H -3.98599300-1.96382400-1.39178200 O 0.23296100 0.45564900-0.52368700 Al 1.94625900-0.16840400-0.05752200 Cl 3.21120200 1.46779300-0.58355500 Cl 2.11496800-1.92516700-1.24865000 Cl 1.83781800-0.55378800 2.05211800 C -3.97571400-0.72521500 0.54307900 23

H -4.26212500 0.26056000 0.15221500 H -4.88504100-1.13970600 1.00563600 C -0.32487300 2.22690100 1.01292100 H -1.21037300 2.77924400 1.32364900 H 0.09808900 1.66109500 1.84872700 H 0.44952500 2.93573300 0.68652600 F -2.74091900 2.30444800-0.39858400 Catalyzed Product_F_endo-cis (R1=F) C -1.96550900-1.91327500-0.22505300 C -1.69502400-1.38823400 1.00558500 C -2.59712500-0.29629200 1.21204100 C -2.01452800 1.11478300-0.48190500 C -2.43886700 0.17498700-1.55543800 C -3.06554600-1.13583100-0.87099400 H -1.38251100-2.67872400-0.72661000 H -0.85596600-1.64148000 1.64255700 H -2.61092600 0.33043800 2.09802000 C -0.67767900 1.26015400-0.05045900 H -1.60408600-0.09767600-2.20246400 H -3.21930800 0.64859900-2.15634100 H -3.66257100-1.68729100-1.59974600 O 0.14224500 0.35830300-0.44874500 Al 1.85839500-0.18991300-0.04749000 Cl 3.15345700 1.42738800-0.58047400 Cl 2.08027100-1.95806800-1.23001100 Cl 1.81615800-0.58863900 2.07372200 C -3.80700700-0.55377300 0.35403800 H -4.41312400 0.33058000 0.14382200 H -4.44409600-1.31627500 0.82427700 C -0.24683500 2.36158300 0.86715500 H -1.07173900 3.03129000 1.11147300 H 0.17218600 1.92973700 1.78378700 H 0.56024400 2.92827000 0.38832100 F -2.84812600 2.17318800-0.27127900 Catalyzed TS_F_endo-cis (R1=F) C -1.92691200-1.92459600-0.21884300 C -1.66565900-1.45569700 1.10157500 C -2.66378500-0.59448800 1.47304900 C -1.82009900 1.29165000-0.74636300 C -2.20841900 0.37828700-1.71780500 C -3.06375100-1.29061800-0.72869600 H -1.28803600-2.60916600-0.76635700 H -0.78417900-1.69989900 1.68282100 H -2.72714800-0.05982900 2.41413900 C -0.55725800 1.28954900-0.11431000 H -1.42611500-0.15134300-2.24446400 H -3.10945700 0.59776600-2.28119100 H -3.61405000-1.66520800-1.58594600 O 0.27060900 0.38266600-0.49158700 Al 1.97410500-0.17703300-0.06251500 Cl 3.27880400 1.43515800-0.58755600 24

Cl 2.18424500-1.95118400-1.24202500 Cl 1.91659200-0.58278800 2.05604400 C -3.74174900-0.58526300 0.43286300 H -4.14919200 0.40635500 0.21916300 H -4.58565400-1.20508100 0.77777900 C -0.17189300 2.32052000 0.90065400 H -1.00779200 2.97176600 1.15653400 H 0.21229400 1.82620400 1.79934700 H 0.65066700 2.92340200 0.49535200 F -2.72625700 2.22321200-0.34049200 Catalyzed Reactant_F_exo-cis (R1=F) C 4.19632900-0.73221100 0.18110600 C 3.43656700-0.18961100 1.30580900 C 2.27060800-0.87088000 1.43213000 C 1.75208000 1.28013600-1.09052900 C 2.00103800 0.51242200-2.15989200 C 3.49593200-1.74614000-0.38243600 H 5.16752900-0.36719800-0.13646000 H 3.77543500 0.62528900 1.93652300 H 1.50659800-0.73229100 2.18836900 C 0.53403300 1.21928900-0.28569400 H 2.92588700 0.61985800-2.71312400 H 1.26096600-0.20313100-2.49496700 H 3.80367000-2.35994600-1.22129700 O -0.32947800 0.36284600-0.61196000 Al -2.01734000-0.21238500 0.00668500 Cl -1.66604600-0.66276600 2.07550300 Cl -2.37209500-1.91455100-1.21798800 Cl -3.28034800 1.47604900-0.32543400 C 2.21770800-1.95094500 0.38687900 H 1.31805400-1.90058300-0.24241100 H 2.18865600-2.94733300 0.85525500 C 0.29869300 2.20328000 0.81221400 H 1.20463300 2.74528900 1.07801600 H -0.46306500 2.91579600 0.46450400 H -0.12163400 1.69247900 1.68367200 F 2.65702400 2.18815900-0.67252100 Catalyzed Product_F_exo-cis (R1=F) C 4.20795000-0.74866600 0.06004100 C 3.62933800-0.15851400 1.11739500 C 2.14425700-0.23586600 0.89170800 C 1.93891600 0.79379900-0.39927100 C 2.42987800-0.05778300-1.58101400 C 3.11298300-1.27357300-0.85991900 H 5.27006400-0.79039400-0.16038800 H 4.10556800 0.40085600 1.91372300 H 1.48376900-0.03540400 1.73583500 C 0.51645700 1.16484000-0.23364500 H 3.10824200 0.53976200-2.19369100 H 1.59865900-0.40388200-2.20139500 H 3.40621900-2.07050200-1.54590800 25

O -0.34061200 0.34811000-0.64518700 Al -2.02685200-0.22171600-0.01913500 Cl -1.59764200-0.64112400 2.04726300 Cl -2.38442800-1.94926900-1.19809900 Cl -3.33696400 1.43171700-0.31465600 C 2.00816600-1.59331500 0.17168100 H 1.02805800-1.78187800-0.27225500 H 2.26696000-2.41599900 0.84141800 C 0.15178200 2.35068900 0.59898700 H 1.02031000 2.96270100 0.83358100 H -0.60803400 2.94257300 0.07726100 H -0.31901000 1.98592700 1.52191500 F 2.73012700 1.93195700-0.29543100 Catalyzed TS_F_exo-cis (R1=F) C 4.01559200-0.65701100 0.08446300 C 3.41420000-0.22754000 1.29887300 C 2.14182400-0.74244400 1.37838200 C 1.73830300 1.12517100-0.89616100 C 2.17321300 0.17459000-1.80751700 C 3.08390500-1.37788900-0.66957900 H 5.01673400-0.39390600-0.24030100 H 3.87983700 0.43178200 2.02238000 H 1.42828600-0.59297300 2.18068200 C 0.46234700 1.19660600-0.28765600 H 3.04758500 0.40920300-2.40307700 H 1.42343300-0.45520000-2.27211100 H 3.35350400-2.00769800-1.51140400 O -0.42576200 0.34183900-0.65192700 Al -2.07709100-0.20106300-0.02842700 Cl -1.70008200-0.65346300 2.05137700 Cl -2.46978400-1.94150300-1.20302600 Cl -3.42437900 1.43392800-0.31962400 C 1.91990300-1.69401600 0.24816900 H 0.92329700-1.65274000-0.19645800 H 2.04488400-2.72346800 0.62433600 C 0.12307600 2.29437000 0.67516900 H 0.99163000 2.90387300 0.92248600 H -0.65448000 2.92587900 0.22780200 H -0.30651600 1.86322000 1.58562500 F 2.65867600 2.03974900-0.49869000 Uncatalyzed Reactant_F_endo-cis (R2=F) C 0.23311400 1.70137200 0.29536100 C -0.75777100 1.24603100-0.47534400 C -1.83218600 0.43145900 0.13585500 C -2.96965000 0.00188300-0.77394600 O -1.81877000 0.12292900 1.32109900 H -3.71402000 0.80767500-0.82008500 H -2.63090800-0.19368400-1.79596400 H -3.45232900-0.88460100-0.35989100 C 1.98504300-0.75440900 0.63198600 C 0.96631800-1.48924200 1.12923300 26

C 0.21802700-2.08821200 0.02115000 C 0.77538400-1.71243000-1.15052400 C 1.97609300-0.84764200-0.87081300 H 2.72275800-0.19762300 1.19732400 H 0.71445100-1.61842500 2.17518700 H -0.65170100-2.72311900 0.14611700 H 0.45526300-2.00059400-2.14482400 H 2.89920700-1.31351000-1.24781600 H 1.91997300 0.13773100-1.35086500 H -0.75293700 1.43328500-1.54390300 H 0.28459300 1.56762200 1.36796300 F 1.27550800 2.37530200-0.21319800 Uncatalyzed Product_F_endo-cis (R2=F) C 0.63427400 1.06785800 0.36216500 C -0.37989700 0.46489600-0.64196000 C -1.70131000 0.19710400 0.05289500 C -2.96633000 0.02279500-0.76694100 O -1.72543900 0.02028300 1.26027000 H -3.76304100 0.63515600-0.33478600 H -2.84040300 0.27689400-1.82178900 H -3.28907300-1.02117600-0.68827300 C 1.61297700-0.11011200 0.60850800 C 0.86031000-1.31926700 1.15028800 C 0.16630000-1.87029000 0.14629700 C 0.33294000-0.94571300-1.04760000 C 1.81402100-0.54832800-0.86533600 H 2.49601700 0.19657100 1.17220900 H 0.85173200-1.61872000 2.19138100 H -0.53102900-2.69801300 0.20964400 H 0.02093200-1.32130400-2.02347100 H 2.48955200-1.40112900-0.96532000 H 2.13833400 0.26999900-1.51301900 H -0.49001200 1.10215000-1.52513800 H 0.15612000 1.45376000 1.26317000 F 1.36295100 2.12339300-0.21394200 Uncatalyzed TS_F_endo-cis (R2=F) C 0.50221800 1.36165600 0.35007000 C -0.57826600 1.04276800-0.48714000 C -1.68265700 0.35409800 0.11164500 C -2.91721700 0.04141700-0.71980700 O -1.62526000-0.00226300 1.30487200 H -3.74855600 0.66773200-0.37730200 H -2.76814200 0.21833600-1.78828800 H -3.21271400-0.99896800-0.55859100 C 1.60429300-0.21018300 0.60766000 C 0.79979900-1.23980100 1.14975100 C 0.20633800-1.97281700 0.09535700 C 0.66549400-1.48875700-1.10607000 C 1.82836900-0.57687800-0.85540200 H 2.39987600 0.24730800 1.19023100 H 0.60429400-1.39794000 2.20202300 27

H -0.55889600-2.72847100 0.22547600 H 0.35708300-1.82663600-2.08845600 H 2.76172600-1.15807400-0.92821200 H 1.92294800 0.27307900-1.53237400 H -0.56288300 1.32250300-1.53353800 H 0.30693200 1.56184200 1.39950300 F 1.43668700 2.21870800-0.16953700 Uncatalyzed Reactant_F_exo-cis (R2=F) C -2.41954800-0.34273000-0.29640200 C -1.63554200-1.31670600-1.05628000 C -0.73713100-1.90513000-0.23388500 C 0.92251700 0.85045600-0.61168800 C 0.08264300 1.60246600 0.10580200 C -1.99835400-0.33758200 0.98843200 H -3.19827300 0.28255800-0.71825000 H -1.76747300-1.52014700-2.11365400 H -0.02420100-2.67759600-0.49715300 C 2.03188200 0.12816900 0.04556500 H 0.15020700 1.74465100 1.17735300 H -2.38900700 0.27141300 1.79507300 O 2.12079100 0.02080500 1.26447600 C -0.90556000-1.35677900 1.15594400 H 0.02207600-0.93501100 1.56407000 H -1.20781300-2.15063100 1.85662200 C 3.07320400-0.47308100-0.87865700 H 3.56491300 0.31727400-1.45808500 H 3.81753600-1.01455100-0.29415900 H 2.59954600-1.15010200-1.59864100 H 0.80285900 0.78623900-1.68764600 F -0.91005800 2.29250700-0.46600600 Uncatalyzed Product_F_exo-cis (R2=F) C -2.35330300-0.26965000-0.38480000 C -1.60016800-1.13717200-1.07381100 C -0.28435300-1.28816200-0.32811400 C 0.49034100 0.10013600-0.49603300 C -0.41028500 1.06615100 0.32893200 C -1.55945900 0.15570600 0.84297500 H -3.30844700 0.14919000-0.67769300 H -1.81344800-1.57122600-2.04443200 H 0.31828800-2.16476500-0.57514400 C 1.89832300-0.05123300 0.07036700 H 0.15248400 1.50567400 1.15680500 H -2.13076000 0.59548400 1.66225300 O 2.12180200 0.06276600 1.26438300 C -0.76665100-1.13891300 1.13486800 H 0.04744400-1.00434500 1.85077900 H -1.41374700-1.96098900 1.44866400 C 3.01160000-0.40752400-0.89744700 H 3.37090400 0.51008200-1.38028800 H 3.84141300-0.85992000-0.35229000 H 2.66602600-1.07560800-1.69229400 28

H 0.52571600 0.40517200-1.54521100 F -0.91221600 2.11396100-0.44339600 Uncatalyzed TS_F_exo-cis (R2=F) C -2.35247400-0.21528900-0.34097800 C -1.65350500-1.20714500-1.05105100 C -0.59220800-1.65237100-0.27449100 C 0.68180100 0.57281400-0.52240900 C -0.23942400 1.30704500 0.23287000 C -1.67736200 0.04165000 0.86986200 H -3.17776100 0.36841600-0.73068200 H -1.85803100-1.50973400-2.07184100 H 0.10681800-2.43349500-0.54978900 C 1.91635300 0.08437400 0.08076800 H 0.05197500 1.64655600 1.22340700 H -2.13349700 0.60436000 1.67903900 O 2.09607700 0.05907700 1.30202400 C -0.77886900-1.14955400 1.12518700 H 0.14251900-0.94080600 1.67317000 H -1.34949400-1.90217200 1.69382000 C 3.00970600-0.38116600-0.87069600 H 3.47003800 0.48628400-1.35885600 H 3.77742300-0.91507600-0.30879600 H 2.60882400-1.02265400-1.66222700 H 0.58832600 0.58282000-1.60192400 F -0.98665100 2.24008200-0.43287600 29